CN103923316B - A kind of carbon nano ring graft modification PBO polymkeric substance and preparation method thereof - Google Patents
A kind of carbon nano ring graft modification PBO polymkeric substance and preparation method thereof Download PDFInfo
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- ZVWBTKYLZRDNRH-UHFFFAOYSA-N C[N]1(C)CC(CCC2CC2)C1 Chemical compound C[N]1(C)CC(CCC2CC2)C1 ZVWBTKYLZRDNRH-UHFFFAOYSA-N 0.000 description 1
Abstract
A kind of carbon nano ring graft modification PBO polymkeric substance and preparation method thereof, the present invention relates to modification PBO polymkeric substance and preparation method thereof.The present invention will solve the low technical problem of the tensile strength of existing pbo fiber.The structural formula of a kind of carbon nano ring graft modification PBO polymkeric substance of the present invention is as follows:
wherein A is carbon nano ring, n=30 ~ 100, s=30 ~ 100.Method for making: add in poly phosphoric acid solution by carboxylated carbon nano ring, obtains the dispersion soln of carboxylated carbon nano ring; By PBO polymkeric substance and methylsulfonic acid mix and blend, obtain PBO solution; Carboxylated carbon nano ring dispersion liquid is mixed with PBO solution, after reacting by heating, through washing, drying, obtains carbon nano ring graft modification PBO polymkeric substance.The tensile strength of this polymkeric substance is increased to 8 ~ 9GPa, can be used for producing heat-resistant textiles or as fiber reinforced material.
Description
Technical field
The present invention relates to modification PBO polymkeric substance and preparation method thereof.
Background technology
Polyparaphenylene Ben Bing bis-oxazole (PBO) entrusts Stanford Research Institute of U.S. SRI to test room the beginning of the sixties in last century by United States Air Force material laboratory at first, in order to meet aerospace material needs and design and prepare polymkeric substance, this polymkeric substance is high temperature resistant, high-performance polymer.Be described as 21 century super fiber.In existing man-made fiber, tensile property is the highest, does not exceed only steel fiber, and can outmatch on carbon fiber.Its intensity, modulus are 2 times of Kafra fiber, and have the performance of heat-proof combustion-resistant.Diameter is that the PBO filament of 1mm can be sling the weight of 450kg.In addition, the shock-resistance of pbo fiber, rub resistance and dimensional stability are all very excellent, and light weight and soft.Have a wide range of applications in the field such as aerospace vehicle, guided missile, opportunity of combat, bullet proof clothing, bulletproof halmet and protective garment for high-temp working, optical fiber, rope, sports equipment.But at present, the tensile strength of the pbo fiber prepared is 5.5 ~ 5.8GPa, also there is a big difference with the intensity of Theoretical Calculation, is badly in need of improving.
Summary of the invention
The present invention will solve the low technical problem of the tensile strength of existing pbo fiber, and provides kind of carbon nano ring graft modification PBO polymkeric substance and preparation method thereof.
The structural formula of a kind of carbon nano ring graft modification PBO polymkeric substance of the present invention is as follows:
Wherein A is carbon nano ring, n=30 ~ 100, and s=30 ~ 100, n, s all represent the polymerization degree.
The preparation method of above-mentioned carbon nano ring graft modification PBO polymkeric substance, carries out according to the following steps:
One, add in phosphoric acid by Vanadium Pentoxide in FLAKES, stirring and dissolving obtains poly phosphoric acid solution;
Two, carboxylated carbon nano ring is added in poly phosphoric acid solution prepared by step one, stir 0.5 ~ 2 hour, obtain the dispersion soln of carboxylated carbon nano ring;
Three, by PBO polymkeric substance and methylsulfonic acid mix and blend 4 ~ 24 hours, PBO solution is obtained;
Four, the PBO solution that the carboxylated carbon nano ring dispersion liquid and the step 3 that step 2 are obtained obtain mixes, then stirring reaction 12 ~ 48 hours at 100 DEG C ~ 180 DEG C temperature, obtain reaction product, by dry after reaction product washing, the carbon nano ring graft modification PBO polymkeric substance obtained.
For the carbon nano ring be made up of 10 phenyl ring, the preparation process of carbon nano ring graft modification PBO polymkeric substance of the present invention is described, this preparation process can be represented by the formula:
PPA wherein represents poly phosphoric acid solution, and MSA represents methylsulfonic acid;
for carboxylated carbon nano ring;
The present invention adopts carbon nano ring to carry out graft modification to PBO polymkeric substance, and the tensile strength of the carbon nano ring graft modification PBO polymkeric substance obtained is increased to 8 ~ 9GPa, compared with existing PBO polymer fiber, improves 30% ~ 55%.
Accompanying drawing explanation
Fig. 1 tests the carbon nano ring graft modification PBO polymeric infrared light spectrogram of 1 preparation.
Embodiment
Embodiment one: the structural formula of a kind of carbon nano ring graft modification PBO polymkeric substance of present embodiment is as follows:
Wherein A is carbon nano ring, n=30 ~ 100, s=30 ~ 100.
In present embodiment, n, s all represent the polymerization degree.
Embodiment two: present embodiment and embodiment one unlike the structural representation of carbon nano ring A are:
m is wherein 1 ~ 100, represents the polymerization degree.Other is identical with embodiment one.
Embodiment three: present embodiment and embodiment one unlike the structural representation of carbon nano ring A are:
m is wherein 1 ~ 95, represents the polymerization degree.Other is identical with embodiment one.
Embodiment four: the preparation method of the carbon nano ring graft modification PBO polymkeric substance described in embodiment one, carry out according to the following steps:
One, add in phosphoric acid by Vanadium Pentoxide in FLAKES, stirring and dissolving obtains poly phosphoric acid solution;
Two, carboxylated carbon nano ring is added in poly phosphoric acid solution prepared by step one, stir 0.5 ~ 2 hour, obtain the dispersion soln of carboxylated carbon nano ring;
Three, by PBO polymkeric substance and methylsulfonic acid mix and blend 4 ~ 24 hours, PBO solution is obtained;
Four, the PBO solution that the carboxylated carbon nano ring dispersion liquid and the step 3 that step 2 are obtained obtain mixes, then stirring reaction 12 ~ 48 hours at 100 DEG C ~ 180 DEG C temperature, obtain reaction product, by dry after reaction product washing, the carbon nano ring graft modification PBO polymkeric substance obtained.
Embodiment five: present embodiment and embodiment four are 1:(1 ~ 2 unlike the mass ratio of Vanadium Pentoxide in FLAKES in step one and phosphoric acid); Other is identical with embodiment four.
Embodiment six: present embodiment and embodiment four or five are 1:(50 ~ 1000 unlike the mass ratio of carbon nano ring carboxylated in step 2 and poly phosphoric acid solution); Other is identical with embodiment four or five.
Embodiment seven: one of present embodiment and embodiment four to six are 1:(20 ~ 100 unlike the mass ratio of PBO polymkeric substance and methylsulfonic acid in step 3); Other is identical with one of embodiment four to six.
Embodiment eight: one of present embodiment and embodiment four to seven are 1:(1 ~ 2 unlike the mass ratio of carbon nano ring dispersion liquid carboxylated in step 4 and PBO solution).Other is identical with one of embodiment four to seven.
Embodiment nine: one of present embodiment and embodiment four to eight are carried out according to the following steps unlike the preparation method of carbon nano ring carboxylated in step 2:
A, carbon nano ring is joined in mixing acid, be warming up to 90 ~ 100 DEG C, at this temperature stirring reaction 40 ~ 48 hours, then be cooled to room temperature, obtain mixture solution; Wherein mixing acid is 1:(3 ~ 4 by concentrated nitric acid and the vitriol oil by volume) mix; Ratio 1g:(40mL ~ the 50mL of the quality of carbon nano ring and the volume of mixing acid);
Distilled water is added in b, the mixture solution that obtains to step a, stir after 30 ~ 50 minutes, by millipore filtration suction filtration, then distilled water rinse throw out is used, until suction filter lower end leaches the pH value of liquid in neutral, then by solid formation vacuum drying at 80 ~ 90 DEG C, carboxylated carbon nano ring is obtained.Other is identical with one of embodiment four to eight.
Embodiment ten: one of present embodiment and embodiment four to nine, unlike the preparation method of the PBO polymkeric substance in step 3, are carried out according to the following steps:
1., in a nitrogen atmosphere, massfraction to Vanadium Pentoxide in FLAKES is add 4 in the poly phosphoric acid solution of 83.7%, 6-diamino resorcin hydrochlorate, terephthalic acid and tindichloride, stir to obtain mixture A, then mixture A heated and stirred at 60 DEG C ~ 80 DEG C is reacted 12 ~ 36 hours, obtain mixture B;
2. the mixture B, by step 1. obtained is warming up to 110 ~ 120 DEG C, then adds Vanadium Pentoxide in FLAKES, then insulated and stirred is reacted 5 ~ 6 hours, obtains mixture C;
3. the mixture C, by step 2. obtained is warming up to 150 DEG C, then insulation reaction 5 ~ 6 hours, then is warming up to 180 DEG C, insulation reaction 5 ~ 6 hours, and then after reaction product is cooled to room temperature, be washed to neutrality, vacuum-drying 20 ~ 24 hours at 70 ~ 80 DEG C again, obtains PBO polymkeric substance.Other is identical with one of embodiment four to nine.
Embodiment 11: present embodiment and embodiment ten unlike step 1. in the mol ratio of 4,6-diaminoresorcinol hydrochloride and terephthalic acid be 1:1, they are monomer; Other is identical with embodiment ten.
Embodiment 12: present embodiment and embodiment ten or 11 unlike step 1. in the mass ratio of tindichloride and terephthalic acid be 0.003:1; Other is identical with embodiment ten or 11.
Embodiment 13: 1. the middle total mass of 4,6-diaminoresorcinol hydrochloride, terephthalic acid and tindichloride and the mass ratio of poly phosphoric acid solution are 0.2:1 unlike step for one of present embodiment and embodiment ten to ten two; Other is identical with one of embodiment two to ten two.
Embodiment 14: one of present embodiment and embodiment two to ten three unlike step 2. in the Vanadium Pentoxide in FLAKES that adds and step 1. in the mol ratio of terephthalic acid monomers be 1:0.7 ~ 0.8; Other is identical with one of embodiment ten to ten three.
With following verification experimental verification beneficial effect of the present invention:
Test 1: first prepare carbon nano ring, concrete steps are as follows:
One, in 500mL round-bottomed flask, add the 4'-bromo-(1 of 50.5g, 1'-biphenyl)-4-alcohol, and 0 DEG C, add the trimethylchlorosilane of 22.1g imidazoles, 300ml methylene dichloride and 33ml under the condition that stirs, then mixing solutions is stirred 16h at ambient temperature, under in whipping process, the concentration adding 150ml is 1mol/L sodium bicarbonate aqueous solution, solution layering, be divided into organic layer and water layer, by organic layer washed with water, by dry for organic layers with sodium sulfate also concentrating under reduced pressure, be pale solid A;
Two, 5g pale solid A is joined in the round-bottomed flask of 250ml, the acetonitrile solution of the tetrahydrofuran (THF) of 80ml, 35ml deionized water and 20ml is added when stirring, add 7.5g (diacetoxy iodine) benzene afterwards in the solution slowly, stirring reaction 16h, obtains orange solid B by reaction product concentrating under reduced pressure;
Three, the sodium hydride of 3.9g is joined in the round-bottomed flask of 2L, and add the tetrahydrofuran (THF) of 400mL, mixing solutions is cooled to subzero-78 DEG C, slowly adds the tetrahydrofuran solution of solid B and 200mL of 20.0g at such a temperature, stirring reaction 2h, obtains solution M;
On the other hand, in 500mL round-bottomed flask, add 34.7g 4-bromochlorophene and 200mL tetrahydrofuran (THF) obtain mixing solutions, under the condition stirred, add the hexane solution that 73.9mL concentration is 2.5mol/L n-Butyl Lithium, at subzero-78 DEG C, react 0.5h, obtain solution C; After obtaining solution C, solution C is transferred in the round-bottomed flask of the 2L filling solution M, mix and blend, be evaporated to the volume half of solution, obtain brown solution D;
Four, the sodium hydride of 7.84g, 400mL tetrahydrofuran solution are joined in 1L round-bottomed flask, add 200ml brown solution D afterwards, 0.5h is stirred at 0 DEG C, in the solution of the reaction afterwards methyl-iodide of 18.8ml added, at room temperature stir 16h, the mixing solutions dried over sodium sulfate obtained concentrating under reduced pressure, obtain a kind of yellow solid, with hexane, yellow solid is carried out recrystallization, obtain white crystals E;
Five, 2g white crystals E is dissolved in the middle of the tetrahydrofuran solution of 56mL, and be cooled to subzero-78 DEG C, add the hexane solution that 3mL concentration is 2.5mol/L n-Butyl Lithium, add the isopropyl alcohol boric acid of 2mL subsequently at once, stir 0.5h, obtain product F with chromatography purification;
Six, by the Pd (PPh of white crystals E, 0.312g of product F, 1.27g of 1.96g
3)
4join in 250mL three-necked bottle, the mass percentage concentration adding 44mL afterwards again in reactor is the sodium bicarbonate aqueous solution of 0.5mol/L and 150mL concentration is the isopropanol water solution of 1mol/L, afterwards by reaction soln stirring reaction 16 hours at 85 DEG C, obtain carbon nano ring.
The structural formula of the carbon nano ring that this test obtains is as follows:
m=0 ~ 3 wherein.The carbon nano ring obtained with this test carries out following test.
Test 2: the preparation method of the carbon nano ring graft modification PBO polymkeric substance of this test, carry out according to the following steps:
The preparation of one, carboxylated carbon nano ring: concrete grammar is as follows:
A, 2g carbon nano ring is joined in mixing acid, be warming up to 100 DEG C, at this temperature stirring reaction 48 hours, then be cooled to room temperature, obtain mixture solution; Wherein mixing acid by concentrated nitric acid and the vitriol oil by volume for 1:3 mixes; The ratio 1g:50mL of the quality of carbon nano ring and the volume of mixing acid;
Add distilled water in b, the mixture solution that obtains to step a, stir after 30 minutes, by millipore filtration suction filtration, then distilled water rinse throw out is used, until suction filter lower end leaches the pH value of liquid in neutral, then by solid formation vacuum drying at 90 DEG C, obtain carboxylated carbon nano ring.
Two, the preparation of PBO polymkeric substance: concrete grammar is as follows:
1., in a nitrogen atmosphere, massfraction to Vanadium Pentoxide in FLAKES is add 4 in the poly phosphoric acid solution of 83.7%, 6-diamino resorcin hydrochlorate, terephthalic acid and tindichloride, stir to obtain mixture A, then mixture A heated and stirred at 70 DEG C is reacted 20 hours, obtain mixture B; Wherein the mol ratio of 4,6-diaminoresorcinol hydrochloride and terephthalic acid is 1:1, and they are monomer; The mass ratio of tindichloride and terephthalic acid is 0.003:1; The total mass of 4,6-diaminoresorcinol hydrochloride, terephthalic acid and tindichloride and the mass ratio of poly phosphoric acid solution are 0.2:1;
2. the mixture B, by step 1. obtained is warming up to 120 DEG C, then adds Vanadium Pentoxide in FLAKES, then insulated and stirred reacts 6 hours, obtains mixture C; In the Vanadium Pentoxide in FLAKES wherein added and step a, the mol ratio of terephthalic acid monomers is 1:0.8;
3. the mixture C, by step 2. obtained is warming up to 150 DEG C, then insulation reaction 5 hours, then is warming up to 180 DEG C, insulation reaction 5 hours, and then after reaction product is cooled to room temperature, be washed to neutrality, vacuum-drying 24 hours at 80 DEG C again, obtains PBO polymkeric substance.
Three, the preparation of carbon nano ring graft modification PBO polymkeric substance, concrete steps are as follows:
(1), 193.34g Vanadium Pentoxide in FLAKES being added to 145.55g mass percentage concentration is that in the phosphoric acid of 85%, stirring and dissolving obtains poly phosphoric acid solution;
(2), by carbon nano ring carboxylated for 0.5g add in poly phosphoric acid solution prepared by step (), stir 1 hour, obtain the dispersion soln of carboxylated carbon nano ring;
(3), by 10gPBO polymkeric substance and 338.89g methylsulfonic acid mix and blend 12 hours, PBO solution is obtained;
(4) the PBO solution that the carboxylated carbon nano ring dispersion liquid, step (two) obtained and step (three) obtain mixes, then stirring reaction 24 hours at 130 DEG C of temperature, obtain reaction product, reaction product to be added in 2L water agitator treating 24 hours, drying, the carbon nano ring graft modification PBO polymkeric substance obtained.
The carbon nano ring graft modification PBO polymkeric substance this test obtained carries out Infrared spectroscopy, and as shown in Figure 1, as can be seen from Figure 1, have two of carbon nano ring obvious absorption peaks in spectrogram, one is at 1554cm to the infrared spectrogram obtained
-1neighbouring-C=C-stretching vibration peak, another is at 1124cm
-1near, i.e. C-C stretching vibration.3068cm
-1peak be C-H on aromatic ring, secondly have 845cm in fingerprint region
-1there is the peak of obvious phenyl ring.At 1628cm
-1c=N peak, 1050cm
-1-C-O-C peak and-3068cm
-1aromatic ring on C-H, be the charateristic avsorption band of PBO.Infrared spectrum indicates carbon nano ring and the successful copolymerization of PBO together.
After the carbon nano ring graft modification PBO polymkeric substance drawing fiber this test obtained, carry out tensile strength test with stretching testing machine, test result shows, the tensile strength of carbon nano ring graft modification PBO polymer fiber is 8.3GPa.
Test 3: the preparation method of the carbon nano ring graft modification PBO polymkeric substance of this test, carry out according to the following steps:
The preparation of one, carboxylated carbon nano ring: concrete grammar is as follows:
A, 2g carbon nano ring is joined in mixing acid, be warming up to 100 DEG C, at this temperature stirring reaction 48 hours, then be cooled to room temperature, obtain mixture solution; Wherein mixing acid by concentrated nitric acid and the vitriol oil by volume for 1:4 mixes; The ratio 1g:50mL of the quality of carbon nano ring and the volume of mixing acid;
Add distilled water in b, the mixture solution that obtains to step a, stir after 50 minutes, by millipore filtration suction filtration, then distilled water rinse throw out is used, until suction filter lower end leaches the pH value of liquid in neutral, then by solid formation vacuum drying at 90 DEG C, obtain carboxylated carbon nano ring.
Two, the preparation of PBO polymkeric substance: concrete grammar is as follows:
1., in a nitrogen atmosphere, massfraction to Vanadium Pentoxide in FLAKES is add 4 in the poly phosphoric acid solution of 83.7%, 6-diamino resorcin hydrochlorate, terephthalic acid and tindichloride, stir to obtain mixture A, then mixture A heated and stirred at 80 DEG C is reacted 30 hours, obtain mixture B; Wherein the mol ratio of 4,6-diaminoresorcinol hydrochloride and terephthalic acid is 1:1, and they are monomer; The mass ratio of tindichloride and terephthalic acid is 0.003:1; The total mass of 4,6-diaminoresorcinol hydrochloride, terephthalic acid and tindichloride and the mass ratio of poly phosphoric acid solution are 0.2:1;
2. the mixture B, by step 1. obtained is warming up to 120 DEG C, then adds Vanadium Pentoxide in FLAKES, then insulated and stirred reacts 6 hours, obtains mixture C; In the Vanadium Pentoxide in FLAKES wherein added and step a, the mol ratio of terephthalic acid monomers is 1:0.8;
3. the mixture C, by step 2. obtained is warming up to 150 DEG C, then insulation reaction 5 hours, then is warming up to 180 DEG C, insulation reaction 6 hours, and then after reaction product is cooled to room temperature, be washed to neutrality, vacuum-drying 24 hours at 80 DEG C again, obtains PBO polymkeric substance.
Three, the preparation of carbon nano ring graft modification PBO polymkeric substance, concrete steps are as follows:
(1), 195.23g Vanadium Pentoxide in FLAKES being added to 148.24g mass percentage concentration is that in the phosphoric acid of 85%, stirring and dissolving obtains poly phosphoric acid solution;
(2), by carbon nano ring carboxylated for 0.5g add in poly phosphoric acid solution prepared by step (), stir 1 hour, obtain the dispersion soln of carboxylated carbon nano ring;
(3), by 10gPBO polymkeric substance and 334.57g methylsulfonic acid mix and blend 12 hours, PBO solution is obtained;
(4) the PBO solution that the carboxylated carbon nano ring dispersion liquid, step (two) obtained and step (three) obtain mixes, then stirring reaction 30 hours at 170 DEG C of temperature, obtain reaction product, reaction product to be added in 2L water agitator treating 24 hours, drying, the carbon nano ring graft modification PBO polymkeric substance obtained.
After the carbon nano ring graft modification PBO polymkeric substance drawing fiber this test obtained, carry out tensile strength test with stretching testing machine, test result shows, the tensile strength of carbon nano ring graft modification PBO polymer fiber is 8.83GPa.
Claims (10)
1. a carbon nano ring graft modification PBO polymkeric substance, is characterized in that the structural formula of this polymkeric substance is as follows:
Wherein A is carbon nano ring, n=30 ~ 100, s=30 ~ 100.
2. prepare the method for carbon nano ring graft modification PBO polymkeric substance according to claim 1, it is characterized in that the method is carried out according to the following steps:
One, add in phosphoric acid by Vanadium Pentoxide in FLAKES, stirring and dissolving obtains poly phosphoric acid solution;
Two, carboxylated carbon nano ring is added in poly phosphoric acid solution prepared by step one, stir 0.5 ~ 2 hour, obtain the dispersion soln of carboxylated carbon nano ring;
Three, by PBO polymkeric substance and methylsulfonic acid mix and blend 4 ~ 24 hours, PBO solution is obtained;
Four, the PBO solution that the carboxylated carbon nano ring dispersion liquid and the step 3 that step 2 are obtained obtain mixes, then stirring reaction 12 ~ 48 hours at 100 DEG C ~ 180 DEG C temperature, obtain reaction product, by dry after reaction product washing, obtain carbon nano ring graft modification PBO polymkeric substance.
3. the preparation method of carbon nano ring graft modification PBO polymkeric substance according to claim 2, is characterized in that the mass ratio of Vanadium Pentoxide in FLAKES and phosphoric acid in step one is 1:(1 ~ 2).
4. the preparation method of the carbon nano ring graft modification PBO polymkeric substance according to Claims 2 or 3, is characterized in that the mass ratio of carbon nano ring carboxylated in step 2 and poly phosphoric acid solution is 1:(50 ~ 1000).
5. the preparation method of the carbon nano ring graft modification PBO polymkeric substance according to Claims 2 or 3, is characterized in that the mass ratio of PBO polymkeric substance and methylsulfonic acid in step 3 is 1:(20 ~ 100).
6. the preparation method of the carbon nano ring graft modification PBO polymkeric substance according to Claims 2 or 3, it is characterized in that the preparation method of carbon nano ring carboxylated in step 2 carries out according to the following steps:
A, carbon nano ring is joined in mixing acid, be warming up to 90 ~ 100 DEG C, at this temperature stirring reaction 40 ~ 48 hours, then be cooled to room temperature, obtain mixture solution; Wherein mixing acid is 1:(3 ~ 4 by concentrated nitric acid and the vitriol oil by volume) mix; Ratio 1g:(40mL ~ the 50mL of the quality of carbon nano ring and the volume of mixing acid);
Distilled water is added in b, the mixture solution that obtains to step a, stir after 30 ~ 50 minutes, by millipore filtration suction filtration, then distilled water rinse throw out is used, until suction filter lower end leaches the pH value of liquid in neutral, then by solid formation vacuum drying at 80 ~ 90 DEG C, carboxylated carbon nano ring is obtained.
7. the preparation method of the carbon nano ring graft modification PBO polymkeric substance according to Claims 2 or 3, is characterized in that the preparation method of the PBO polymkeric substance in step 3, carries out according to the following steps:
1., in a nitrogen atmosphere, massfraction to Vanadium Pentoxide in FLAKES is add 4 in the poly phosphoric acid solution of 83.7%, 6-diamino resorcin hydrochlorate, terephthalic acid and tindichloride, stir to obtain mixture A, then mixture A heated and stirred at 60 DEG C ~ 80 DEG C is reacted 12 ~ 36 hours, obtain mixture B;
2. the mixture B, by step 1. obtained is warming up to 110 ~ 120 DEG C, then adds Vanadium Pentoxide in FLAKES, then insulated and stirred is reacted 5 ~ 6 hours, obtains mixture C;
3. the mixture C, by step 2. obtained is warming up to 150 DEG C, then insulation reaction 5 ~ 6 hours, then is warming up to 180 DEG C, insulation reaction 5 ~ 6 hours, and then after reaction product is cooled to room temperature, be washed to neutrality, vacuum-drying 20 ~ 24 hours at 70 ~ 80 DEG C again, obtains PBO polymkeric substance.
8. the preparation method of carbon nano ring graft modification PBO polymkeric substance according to claim 7, is characterized in that the mol ratio of 4,6-diaminoresorcinol hydrochloride and terephthalic acid during step is 1. 1:1.
9. the preparation method of carbon nano ring graft modification PBO polymkeric substance according to claim 7, it is characterized in that 1. the middle total mass of 4,6-diaminoresorcinol hydrochloride, terephthalic acid and tindichloride and the mass ratio of poly phosphoric acid solution are 0.2:1 to step.
10. the preparation method of carbon nano ring graft modification PBO polymkeric substance according to claim 7, is characterized in that during the Vanadium Pentoxide in FLAKES that adds during step 2. and step are 1., the mol ratio of terephthalic acid monomers is 1:0.7 ~ 0.8.
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| CN1478818A (en) * | 2003-07-18 | 2004-03-03 | 哈尔滨工业大学 | Synthesis method of PBO/carbon nanometer pipe composite material |
| CN101274983B (en) * | 2008-05-21 | 2010-06-02 | 哈尔滨工业大学 | Preparation for single wall carbon nano-tube monomer-containing compound for PBO polymerization |
| CN102491309A (en) * | 2011-12-07 | 2012-06-13 | 北京化工大学 | Carbon nanometer ring and preparation method thereof |
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| US7309727B2 (en) * | 2003-09-29 | 2007-12-18 | General Electric Company | Conductive thermoplastic compositions, methods of manufacture and articles derived from such compositions |
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| CN1478818A (en) * | 2003-07-18 | 2004-03-03 | 哈尔滨工业大学 | Synthesis method of PBO/carbon nanometer pipe composite material |
| CN101274983B (en) * | 2008-05-21 | 2010-06-02 | 哈尔滨工业大学 | Preparation for single wall carbon nano-tube monomer-containing compound for PBO polymerization |
| CN102491309A (en) * | 2011-12-07 | 2012-06-13 | 北京化工大学 | Carbon nanometer ring and preparation method thereof |
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